Centimeter-sized two-dimensional (2D) colloidal single crystals of polystyrene (PS) particles were fabricated at the water/air interface by capillary-modulated self-assembly. Different from previous reports, in this work, emulsifier was used to facilitate the stress release during 2D colloidal crystal formation by adjusting the interparticle lateral interactions. With the assistance of compressed nitrogen flow, 2D hexagonal colloidal single crystals of centimeter size were obtained under appropriate emulsifier concentrations. A new method was also developed to transfer the 2D colloidal crystals from the air/water interface to the desired substrate without obvious disturbance. This new transferring method was proven not to be sensitive to surface wettability nor curvature, thus 2D colloidal single crystals with large areas could be obtained on different kinds of substrate.